CN108336409A - A kind of nickelic ternary lithium battery overcharge-prevention electrolyte - Google Patents
A kind of nickelic ternary lithium battery overcharge-prevention electrolyte Download PDFInfo
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- CN108336409A CN108336409A CN201810227144.9A CN201810227144A CN108336409A CN 108336409 A CN108336409 A CN 108336409A CN 201810227144 A CN201810227144 A CN 201810227144A CN 108336409 A CN108336409 A CN 108336409A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to technical fields prepared by ternary battery electrolyte, and in particular to a kind of nickelic ternary lithium battery overcharge-prevention electrolyte.A kind of nickelic ternary lithium battery overcharge-prevention electrolyte of the present invention; under the conditions of overcharging, electropolymerization occurs for 2 fluorine N, N diformazan phenalgins and polyfluoro biphenyl liquid crystal compound object; protective film is formed in electrode surface, the protective film that composition electropolymerization is formed is more complete fine and close compared to the film that single substance is formed.Protective film completely cuts off electrolyte, increases electrode internal resistance, forms open circuit when anode is solid state polymerized object cladding completely, battery is in failure state；Electrolyte ion conductivity of the present invention is high, and up to 0.8 × 10‑2S/cm, for lithium ion transference number close to 1, electrochemically stable potential range is wide, and thermostabilization is good, and use temperature range is wide, and collector and quiet property substance do not chemically react in stable chemical performance, with battery, safety and low toxicity.
Description
Technical field
The invention belongs to technical fields prepared by ternary battery electrolyte, and in particular to a kind of nickelic anti-mistake of ternary lithium battery
Fill electrolyte.
Background technology
Ternary material（Nickle cobalt lithium manganate）The specific capacity of material, therefore nickelic ternary material can be greatly promoted by improving the content of nickel
Expect a kind of ideal material of necessarily large-sized battery in future.
The maximum obstacle for restricting the application of high power capacity power battery at present is exactly the safety of battery, wherein being drawn by overcharge
The lithium ion battery unsafe acts of hair are most dangerous one of factors.For lithium ion battery under overcharge conditions, cell voltage is anxious
Increase severely big, to cause the irreversible change of positive active material structure and the oxygenolysis of electrolyte, and then generates a large amount of
Gas and release a large amount of heat, cause inner pressure of battery and temperature to steeply rise, cause thermal runaway, explosion, burning occurs in battery
Etc. hidden dangers, meanwhile, the Carbon anode surface in overcharging state can also reduce its safety because of the deposition of metal.
Chinese invention patent application number application number 201511000331.6 discloses a kind of Overcharge prevention electrolyte and lithium battery,
The electrolyte includes lithium salts, organic solvent and additive, and additive includes additive S, and additive S is in Overcharge prevention electrolyte
Mass percent is 0.01~20%.The invention improves electrolyte on the basis of generating minor impact to electrolytic conductivity
Overcharge resistance performance energy, improve the cycle efficieny of charge and discharge；The lithium battery prepared by the electrolyte has been likewise supplied with these advantages, right
The performance influence of normal lithium battery is very small, disclosure satisfy that the needs of application.
Chinese invention patent application number application number 201710293086.5 disclose a kind of anti-overcharge lithium battery electrolytes and
Preparation method.A kind of anti-overcharge lithium battery electrolytes of the disclosure of the invention and preparation method thereof, belong to lithium battery material technology
Field, the lithium battery electrolytes are made of lithium salts, double solvents and additive；The lithium salts be inorganic lithium salt, organic boronic lithium,
At least one of lithium salts of sulfonimide；The double solvents is at least two solvents in carbonate-based solvent；It is described to add
It is at least one of sulfurous esters compound, carbonats compound, sulfonates compounds and 2', 4'- diformazan to add agent
Base -2,4- DfBPs；The quality of the additive accounts for the 1%-15% of electrolyte.The invention prepares anti-overcharge lithium battery electrolytes
Oxygenolysis can occur prior to electrolyte when lithium battery overcharges, contact of the partition electrolyte with electrode surface promotes peace
Full performance.
Chinese invention patent application number application number 201611268416.7 discloses a kind of anti-overcharge electrolysis of ternary battery
Liquid consists of the following compositions：Organic solvent, lithium salts, anti-overcharge additive, the anti-overcharge additive occupy the quality of solvent
Than being 3~8%, the anti-overcharge additive is biphenyl and/or cyclohexylbenzene, and the organic solvent is that ethers and esters are organic
Solvent.The present invention also proposes the preparation method of the Overcharge prevention electrolyte.Overcharge prevention electrolyte proposed by the invention, passes through BP
With the immixture of CHB, electropolymerization can be overcharged in over-charging of battery, block being filled with for electric current, effectively avoid ternary power
What lithium battery was brought when overcharging catch fire or explosion phenomenon, to solve the mistake of the ternary battery of puzzlement industry all the time
Fill safety issue.
Chinese invention patent application number application number 201710496466.9 discloses a kind of ternary lithium electricity Overcharge prevention electrolyte
And lithium ion battery, the ternary lithium electricity Overcharge prevention electrolyte, effectively solve the problems, such as on fire from explosion, hair that lithium battery overshoot generates
It is bright to additionally provide a kind of lithium ion battery.The ternary lithium electricity Overcharge prevention electrolyte of the invention, including lithium salts, organic solvent, overcharge
Additive, flame-retardant additive, film for additive.The lithium ion battery of the invention, including cathode sheet, anode pole piece, it is placed in the moon
Isolation film between pole pole piece and anode pole piece and the ternary lithium electricity Overcharge prevention electrolyte.
From the prior art as can be seen that when overcharging additive is biphenyl, in over-charging of battery, aerogenesis additive biphenyl will
It is aggregated in electrode surface and forms SEI films, prevent the migration of lithium ion, improve the internal resistance of cell, so that it is powered off and then improve battery
Security performance.SEI films have electronic isolation, insoluble in electrolyte, have certain mechanical strength, toughness, can drop
The irreversible capacity of low graphite and keep excellent embedding, de- lithium cycle performance.But the film compares the conductivity of lithium ion
It is low, the performance in proper order of battery and storage life can be caused to significantly reduce.Voltolisation mould assembly additive such as biphenyl, cyclohexyl benzene, though it can
Effectively to inhibit over-charging of battery, but its addition can damage the cycle performance of battery.And oxidation-reduction type additive such as ferrocene and
Its derivative, fennel benzene and its derivative etc. fail to reach though it is reversible due to its lower oxidation potential to overcharge protection mechanism
Redox reaction just occurs for lithium ion battery normal working voltage, often limit its different battery material systems lithium from
Large-scale use in sub- battery.Therefore, there is an urgent need for finding a kind of overcharge protection additives, being both avoided that, which makes SEI films overcharge, makes
At safety problem, and be avoided that anti-overcharge additive damage cycle performance of battery and react the relatively low problem of potential.
Invention content
In view of the deficiencies of the prior art, present invention proposition is a kind of can effectively avoid anti-overcharge additive damage circulating battery
The relatively low problem of potential can and be reacted, the nickelic ternary lithium battery overcharge-prevention electrolyte of SEI film overcharge safeties is improved.
To solve the above problems, the present invention uses following technical scheme：
A kind of nickelic ternary lithium battery overcharge-prevention electrolyte, the wherein electrolyte include the solvent of 20~40 parts by weight, 5~20 weights
Measure the solute lithium salts of part, the anti-overcharge additive of 2~10 parts by weight;Wherein, the anti-overcharge additive is by the fluoro- N of 2-, N- bis-
First phenalgin and polyfluoro biphenyl liquid crystal compound object composition.
Further, above-mentioned a kind of nickelic ternary lithium battery overcharge-prevention electrolyte, wherein the electrolyte is by 25~35
The solvent of parts by weight, the solute lithium salts of 10~18 parts by weight, 3~8 parts by weight anti-overcharge additive mixing after be prepared.
Further, above-mentioned a kind of nickelic ternary lithium battery overcharge-prevention electrolyte, wherein the electrolyte is by 30 weight
Part solvent, the solute lithium salts of 15 parts by weight, 5 parts by weight the mixing of anti-overcharge additive after be prepared.
Electrolyte is four big critical material of lithium ion battery（Anode, cathode, diaphragm, electrolyte）One of, it is known as lithium ion
" blood " of battery plays the role of conducting electronics in the battery between positive and negative anodes, is that lithium ion battery obtains high voltage, high ratio
The guarantee of the advantages that energy.Electrolyte generally by raw materials such as the organic solvent of high-purity, electrolyte lithium salt, necessary additives,
Under certain condition, it is formulated by a certain percentage.
Organic solvent is the main part of electrolyte, closely related with the performance of electrolyte, and organic solvent is using preceding necessary tight
Lattice control quality, such as require purity 99.9% or more, moisture must reach 10*l0 -6Below.The purity and stabilization of solvent
There are close ties between voltage, the oxidizing potential of purity organic solvent up to standard is in 5V or so, the oxidizing potential pair of organic solvent
Prevent over-charging of battery, safety from having great significance in research.Further, above-mentioned a kind of nickelic ternary lithium battery overcharge-prevention electrolysis
Liquid, wherein the solvent is glutaronitrile, adiponitrile, dicyandiamide, acetonitrile, malononitrile, p-chlorobenzyl cyanide, the chloro- 5- nitrobenzoyls of 2-
Nitrile, m-trifluoromethyl benzene acetonitrile, cyaniding benzyl, isophthalodinitrile, butyronitrile, acrylonitrile, dimethylaminopropionitrile, propionitrile, hydroxyacetonitrile
At least one of.
Further, above-mentioned a kind of nickelic ternary lithium battery overcharge-prevention electrolyte, wherein the solvent is more preferably penta 2
At least one of nitrile, adiponitrile, malononitrile, butyronitrile, acrylonitrile, hydroxyacetonitrile.
Further, above-mentioned a kind of nickelic ternary lithium battery overcharge-prevention electrolyte, wherein the solute lithium salts is double trifluoros
At least one of sulfonyl methane imine lithium or two (trimethyl fluoride sulfonyl) imine lithiums.
Further, above-mentioned a kind of nickelic ternary lithium battery overcharge-prevention electrolyte, wherein the polyfluoro biphenyl liquid crystal compound
Object is 3,4- difluoros (4 '-propyl dicyclohexyl) biphenyl.
Further, above-mentioned a kind of nickelic ternary lithium battery overcharge-prevention electrolyte, wherein the electrolyte further includes 3~10
Parts by weight flame-retardant additive.
Solvent, lithium salts, anti-overcharge additive and other additives are configured to form electrolysis by the present invention in the form of compositions
Liquid, various additives interact in composition, influence each other, improve the security performances such as the pressure-resistant performance of electrolyte, and not
The shortcomings of conductivity being caused to reduce, can utilize its surface-active to reduce electrolysis if flame-retardant additive can be fluorine-containing fire retardant
Fluid viscosity, solves the problems, such as compatibility at the shortcomings that avoiding previous fire retardant.Meanwhile additive is added in the form of compositions
Workload can be reduced and reduce cost.Further, above-mentioned a kind of nickelic ternary lithium battery overcharge-prevention electrolyte, wherein the resistance
Combustion additive is fluorine-containing flame-retardant additive, more preferably fluoric cyclic carbonate, fluorinated chain carbonate, alkyl-perfluoro alkane
At least one of base ether.
A kind of nickelic ternary lithium battery overcharge-prevention electrolyte of the present invention, under the conditions of overcharging, the fluoro- N of 2-, N- diformazans phenalgin and
Electropolymerization occurs for polyfluoro biphenyl liquid crystal compound object, and protective film, the protective film phase that composition electropolymerization is formed are formed in electrode surface
It is more complete finer and close than the film that single substance is formed.Protective film completely cuts off electrolyte, increases electrode internal resistance, waits for anode completely by solid-state
Open circuit is formed when polymer overmold, battery is in failure state；Electrolyte ion conductivity of the present invention is high, and up to 0.8 × 10-2S/
Cm, for lithium ion transference number close to 1, electrochemically stable potential range is wide, and thermostabilization is good, and use temperature range is wide, chemically
It can stablize, not chemically reacted with collector in battery and quiet property substance, safety and low toxicity.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of nickelic ternary lithium battery overcharge-prevention electrolyte, the electrolyte include the solvent of 30 parts by weight, 10 parts by weight solute
The anti-overcharge additive of lithium salts, 5 parts by weight, 5 parts by weight flame-retardant additives；Solvent is glutaronitrile；Solute lithium salts is double fluoroforms
Alkane sulfimide lithium；The anti-overcharge additive is by the fluoro- N of 2-, N- diformazans phenalgin and polyfluoro biphenyl liquid crystal compound object composition, institute
It is 3,4- difluoros (4 '-propyl dicyclohexyl) biphenyl to state polyfluoro biphenyl liquid crystal compound object；Flame-retardant additive is fluoric cyclic carbonic acid
Ester；
The preparation method of above-mentioned nickelic ternary lithium battery overcharge-prevention electrolyte, includes the following steps：By solvent, solute lithium salts, prevent
Overcharging additive, flame-retardant additive mixing, obtain compositions of additives, are sufficiently stirred at 25 DEG C, obtain electrolyte.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 1 obtains, and is obtained
To simulated battery.
Electrochemical reaction is tested using cyclic voltammetry, the voltage of 0 ~ 6V, takes the EIS frequency ranges to be
100kHz ~ 10MHz, sweep speed 5mV/s, when blanking voltage is 5V carrying out 100% overcharges experiment, and what is obtained the results are shown in Table 1
It is shown；Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, electrolyte prepared by embodiment 1 into
Row conductivity is tested, and obtains the results are shown in Table 1；Cycle performance of battery test, circulating battery are carried out to simulated battery obtained above
Performance test conditions are：In 25 DEG C of environment, constant current and constant-voltage charge are carried out under the current value of 0.5C and the voltage of 4.2V
To electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Embodiment 2
A kind of nickelic ternary lithium battery overcharge-prevention electrolyte, the electrolyte include the solvent of 20 parts by weight, 20 parts by weight solute
The anti-overcharge additive of lithium salts, 6 parts by weight, 8 parts by weight flame-retardant additives；Solvent is adiponitrile；Solute lithium salts is two (trifluoros
Sulfonyloxy methyl) imine lithium；The anti-overcharge additive is by the fluoro- N of 2-, N- diformazans phenalgin and polyfluoro biphenyl liquid crystal compound object group
At；The polyfluoro biphenyl liquid crystal compound object is 3,4- difluoros (4 '-propyl dicyclohexyl) biphenyl；Flame-retardant additive is fluoro chain
Carbonic ester；
The preparation method of above-mentioned nickelic ternary lithium battery overcharge-prevention electrolyte, includes the following steps：By solvent, solute lithium salts, prevent
Overcharging additive, flame-retardant additive mixing, obtain compositions of additives, are sufficiently stirred at 25 DEG C, obtain electrolyte.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 2 obtains, and is obtained
To simulated battery.
Electrochemical reaction is tested using cyclic voltammetry, the voltage of 0 ~ 6V, takes the EIS frequency ranges to be
100kHz ~ 10MHz, sweep speed 5mV/s, when blanking voltage is 5V carrying out 100% overcharges experiment, and what is obtained the results are shown in Table 1
It is shown；Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, electrolyte prepared by embodiment 2 into
Row conductivity is tested, and obtains the results are shown in Table 1；Cycle performance of battery test, circulating battery are carried out to simulated battery obtained above
Performance test conditions are：In 25 DEG C of environment, constant current and constant-voltage charge are carried out under the current value of 0.5C and the voltage of 4.2V
To electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Embodiment 3
A kind of nickelic ternary lithium battery overcharge-prevention electrolyte, the electrolyte include the solvent of 40 parts by weight, 15 parts by weight solute
The anti-overcharge additive of lithium salts, 2 parts by weight, 5 parts by weight flame-retardant additives；Solvent is malononitrile；Solute lithium salts is double fluoroforms
Alkane sulfimide lithium；The anti-overcharge additive is by the fluoro- N of 2-, N- diformazans phenalgin and polyfluoro biphenyl liquid crystal compound object composition；Institute
It is 3,4- difluoros (4 '-propyl dicyclohexyl) biphenyl to state polyfluoro biphenyl liquid crystal compound object；Flame-retardant additive is alkyl-perfluoro alkane
Base ether；
The preparation method of above-mentioned nickelic ternary lithium battery overcharge-prevention electrolyte, includes the following steps：By solvent, solute lithium salts, prevent
Overcharging additive, flame-retardant additive mixing, obtain compositions of additives, are sufficiently stirred at 25 DEG C, obtain electrolyte.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 3 obtains, and is obtained
To simulated battery.
Electrochemical reaction is tested using cyclic voltammetry, the voltage of 0 ~ 6V, takes the EIS frequency ranges to be
100kHz ~ 10MHz, sweep speed 5mV/s, when blanking voltage is 5V carrying out 100% overcharges experiment, and what is obtained the results are shown in Table 1
It is shown；Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, electrolyte prepared by embodiment 3 into
Row conductivity is tested, and obtains the results are shown in Table 1；Cycle performance of battery test, circulating battery are carried out to simulated battery obtained above
Performance test conditions are：In 25 DEG C of environment, constant current and constant-voltage charge are carried out under the current value of 0.5C and the voltage of 4.2V
To electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Embodiment 4
A kind of nickelic ternary lithium battery overcharge-prevention electrolyte, the electrolyte include the solvent of 25 parts by weight, 5 parts by weight solute lithium
The anti-overcharge additive of salt, 8 parts by weight, 3 parts by weight flame-retardant additives；Solvent is dimethylaminopropionitrile；Solute lithium salts be two (
Trimethyl fluoride sulfonyl) imine lithium；The anti-overcharge additive is by the fluoro- N of 2-, N- diformazans phenalgin and polyfluoro biphenyl liquid crystal compound
Object forms；The polyfluoro biphenyl liquid crystal compound object is 3,4- difluoros (4 '-propyl dicyclohexyl) biphenyl；Flame-retardant additive is fluoro
Cyclic carbonate；
The preparation method of above-mentioned nickelic ternary lithium battery overcharge-prevention electrolyte, includes the following steps：By solvent, solute lithium salts, prevent
Overcharging additive, flame-retardant additive mixing, obtain compositions of additives, are sufficiently stirred at 25 DEG C, obtain electrolyte.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 4 obtains, and is obtained
To simulated battery.
Electrochemical reaction is tested using cyclic voltammetry, the voltage of 0 ~ 6V, takes the EIS frequency ranges to be
100kHz ~ 10MHz, sweep speed 5mV/s, when blanking voltage is 5V carrying out 100% overcharges experiment, and what is obtained the results are shown in Table 1
It is shown；Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, electrolyte prepared by embodiment 4 into
Row conductivity is tested, and obtains the results are shown in Table 1；Cycle performance of battery test, circulating battery are carried out to simulated battery obtained above
Performance test conditions are：In 25 DEG C of environment, constant current and constant-voltage charge are carried out under the current value of 0.5C and the voltage of 4.2V
It is 0.1C to electric current, constant-current discharge is carried out under 0.5C multiplying powers to the final voltage of 2.5V, carries out the charging and put that 100 times recycle
Electricity, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Embodiment 5
A kind of nickelic ternary lithium battery overcharge-prevention electrolyte, the electrolyte include the solvent of 28 parts by weight, 18 parts by weight solute
The anti-overcharge additive of lithium salts, 4 parts by weight, 6 parts by weight flame-retardant additives；Solvent is hydroxyacetonitrile；Solute lithium salts is double trifluoros
Sulfonyl methane imine lithium；The anti-overcharge additive is by the fluoro- N of 2-, N- diformazans phenalgin and polyfluoro biphenyl liquid crystal compound object composition；
The polyfluoro biphenyl liquid crystal compound object is 3,4- difluoros (4 '-propyl dicyclohexyl) biphenyl；Flame-retardant additive is alkyl-perfluoro
Alkyl ether；
The preparation method of above-mentioned nickelic ternary lithium battery overcharge-prevention electrolyte, includes the following steps：By solvent, solute lithium salts, prevent
Overcharging additive, flame-retardant additive mixing, obtain compositions of additives, are sufficiently stirred at 25 DEG C, obtain electrolyte.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 5 obtains, and is obtained
To simulated battery.
Electrochemical reaction is tested using cyclic voltammetry, the voltage of 0 ~ 6V, takes the EIS frequency ranges to be
100kHz ~ 10MHz, sweep speed 5mV/s, when blanking voltage is 5V carrying out 100% overcharges experiment, and what is obtained the results are shown in Table 1
It is shown；Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, electrolyte prepared by embodiment 5 into
Row conductivity is tested, and obtains the results are shown in Table 1；Cycle performance of battery test, circulating battery are carried out to simulated battery obtained above
Performance test conditions are：In 25 DEG C of environment, constant current and constant-voltage charge are carried out under the current value of 0.5C and the voltage of 4.2V
To electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Embodiment 6
A kind of nickelic ternary lithium battery overcharge-prevention electrolyte, the electrolyte include the solvent of 35 parts by weight, 16 parts by weight solute
The anti-overcharge additive of lithium salts, 3 parts by weight, 9 parts by weight flame-retardant additives；Solvent is dimethylaminopropionitrile；Solute lithium salts is two
(trimethyl fluoride sulfonyl) imine lithium；The anti-overcharge additive is by the fluoro- N of 2-, N- diformazans phenalgin and polyfluoro biphenyl liquid crystal
Close object composition；The polyfluoro biphenyl liquid crystal compound object is 3,4- difluoros (4 '-propyl dicyclohexyl) biphenyl；Flame-retardant additive is fluorine
For cyclic carbonate；
The preparation method of above-mentioned nickelic ternary lithium battery overcharge-prevention electrolyte, includes the following steps：By solvent, solute lithium salts, prevent
Overcharging additive, flame-retardant additive mixing, obtain compositions of additives, are sufficiently stirred at 25 DEG C, obtain electrolyte.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 6 obtains, and is obtained
To simulated battery.
Electrochemical reaction is tested using cyclic voltammetry, the voltage of 0 ~ 6V, takes the EIS frequency ranges to be
100kHz ~ 10MHz, sweep speed 5mV/s, when blanking voltage is 5V carrying out 100% overcharges experiment, and what is obtained the results are shown in Table 1
It is shown；Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, electrolyte prepared by embodiment 6 into
Row conductivity is tested, and obtains the results are shown in Table 1；Cycle performance of battery test, circulating battery are carried out to simulated battery obtained above
Performance test conditions are：In 25 DEG C of environment, constant current and constant-voltage charge are carried out under the current value of 0.5C and the voltage of 4.2V
To electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Comparative example 1
A kind of nickelic ternary lithium battery overcharge-prevention electrolyte, the electrolyte include the solvent of 30 parts by weight, 10 parts by weight solute
Lithium salts, 5 parts by weight flame-retardant additives；Solvent is glutaronitrile；Solute lithium salts is double trifluoromethanesulfonimide lithiums；Flame-retardant additive
For fluoric cyclic carbonate；
The preparation method of above-mentioned nickelic ternary lithium battery overcharge-prevention electrolyte, includes the following steps：By solvent, solute lithium salts, resistance
Additive mixing is fired, compositions of additives is obtained, is sufficiently stirred at 25 DEG C, obtains electrolyte.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that comparative example 1 obtains, and is obtained
To simulated battery.
Electrochemical reaction is tested using cyclic voltammetry, the voltage of 0 ~ 6V, takes the EIS frequency ranges to be
100kHz ~ 10MHz, sweep speed 5mV/s, when blanking voltage is 5V carrying out 100% overcharges experiment, and what is obtained the results are shown in Table 1
It is shown；Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, electrolyte prepared by comparative example 1 into
Row conductivity is tested, and obtains the results are shown in Table 1；Cycle performance of battery test, circulating battery are carried out to simulated battery obtained above
Performance test conditions are：In 25 DEG C of environment, constant current and constant-voltage charge are carried out under the current value of 0.5C and the voltage of 4.2V
It is 0.1C to electric current, constant-current discharge is carried out under 0.5C multiplying powers to the final voltage of 2.5V, carries out the charging and put that 100 times recycle
Electricity, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Table 1：
| Embodiment | Overcharge test result | Multiplying power discharging 3C/1C | Overcharge peak temperature（℃） | Conductivity（mS/cm） | Discharge specific volume for the first time（mAh/g） | Capacity retention ratio after recycling 200 times（%） |
| Embodiment 1 | It is not quick-fried | 92% | 104 | 7.08 | 238 | 89% |
| Embodiment 2 | It is not quick-fried | 90% | 103 | 7.01 | 237 | 87% |
| Embodiment 3 | It is not quick-fried | 91% | 102 | 7.03 | 236 | 85% |
| Embodiment 4 | It is not quick-fried | 89% | 105 | 7.04 | 240 | 88% |
| Embodiment 5 | It is not quick-fried | 88% | 106 | 7.05 | 235 | 85% |
| Embodiment 6 | It is not quick-fried | 91% | 104 | 7.00 | 230 | 85% |
| Comparative example 1 | Surface is micro- swollen | 87% | 101 | 6.87 | 212 | 63% |
Claims (9)
1. a kind of nickelic ternary lithium battery overcharge-prevention electrolyte, which is characterized in that the electrolyte includes the molten of 20~40 parts by weight
Agent, the solute lithium salts of 5~20 parts by weight, 2~10 parts by weight anti-overcharge additive;Wherein, the anti-overcharge additive be by
The fluoro- N of 2-, N- diformazans phenalgin and polyfluoro biphenyl liquid crystal compound object composition.
2. a kind of nickelic ternary lithium battery overcharge-prevention electrolyte according to claim 1, which is characterized in that the electrolyte is
By being made after the anti-overcharge additive mixing of the solvent of 25~35 parts by weight, the solute lithium salts of 10~18 parts by weight, 3~8 parts by weight
It is standby to form.
3. a kind of nickelic ternary lithium battery overcharge-prevention electrolyte according to claim 2, which is characterized in that the electrolyte is
By being prepared after the anti-overcharge additive mixing of the solvent of 30 parts by weight, the solute lithium salts of 15 parts by weight, 5 parts by weight.
4. according to a kind of any one of claims 1 to 3 nickelic ternary lithium battery overcharge-prevention electrolyte, which is characterized in that institute
It is glutaronitrile, adiponitrile, dicyandiamide, acetonitrile, malononitrile, p-chlorobenzyl cyanide, the chloro- 5- nitrobenzonitriles of 2-, trifluoro to state solvent
At least one in methylbenzeneacetonitrile, cyaniding benzyl, isophthalodinitrile, butyronitrile, acrylonitrile, dimethylaminopropionitrile, propionitrile, hydroxyacetonitrile
Kind.
5. a kind of nickelic ternary lithium battery overcharge-prevention electrolyte according to claim 4, which is characterized in that the solvent is penta
At least one of dintrile, adiponitrile, malononitrile, butyronitrile, acrylonitrile, hydroxyacetonitrile.
6. according to a kind of any one of claims 1 to 3 nickelic ternary lithium battery overcharge-prevention electrolyte, which is characterized in that institute
It is double at least one of trifluoromethanesulfonimide lithiums or two (trimethyl fluoride sulfonyl) imine lithiums to state solute lithium salts.
7. a kind of nickelic ternary lithium battery overcharge-prevention electrolyte according to claim 1, which is characterized in that the polyfluoro biphenyl
Liquid-crystal compounds is 3,4- difluoros (4 '-propyl dicyclohexyl) biphenyl.
8. according to a kind of any one of claims 1 to 3 nickelic ternary lithium battery overcharge-prevention electrolyte, which is characterized in that institute
It further includes 3~10 parts by weight flame-retardant additives to state electrolyte.
9. a kind of nickelic ternary lithium battery overcharge-prevention electrolyte according to claim 8, which is characterized in that the fire-retardant addition
Agent is at least one of fluoric cyclic carbonate, fluorinated chain carbonate, alkyl-perfluoroalkyl ether.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113725488A (en) * | 2021-08-30 | 2021-11-30 | 中汽创智科技有限公司 | Metal battery electrolyte and application thereof |
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2018
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113725488A (en) * | 2021-08-30 | 2021-11-30 | 中汽创智科技有限公司 | Metal battery electrolyte and application thereof |
| CN113725488B (en) * | 2021-08-30 | 2023-07-25 | 中汽创智科技有限公司 | Electrolyte for metal battery and application thereof |
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